Vanadyl sulfate

Vanadyl sulfate
Vanadyl sulfate
Names
IUPAC name
Oxovanadium(2+) sulfate
Other names
Basic vanadium(IV) sulfate
Vanadium(IV) oxide sulfate
Vanadium(IV) oxysulfate
Identifiers
CAS Number
  • 27774-13-6 Anhydrous (green in color) checkY
  • 12439-96-2 Pentahydrate (blue in color)
ECHA InfoCard 100.044.214 Edit this at Wikidata
PubChem CID
  • 34007 Anhydrous
  • 167150 Pentahydrate
RTECS number
  • YW1925000
UNII
  • 6DU9Y533FA Anhydrous (green in color) checkY
CompTox Dashboard (EPA)
  • DTXSID4021428 Edit this at Wikidata
InChI
  • InChI=1S/H2O4S.O.V/c1-5(2,3)4;;/h(H2,1,2,3,4);;/q;;+2/p-2 ☒N
    Key: UUUGYDOQQLOJQA-UHFFFAOYSA-L ☒N
Properties
Chemical formula
H10O10SV
Molar mass 253.07 g·mol−1
Appearance Blue solid
Melting point 105 °C (221 °F; 378 K) decomposes
Solubility in water
Soluble
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
Irritant
Flash point Non-flammble
Related compounds
Other anions
Vanadyl chloride
Vanadyl nitrate
Other cations
Vanadium(III) sulfate
Related compounds
Vanadyl acetylacetonate
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references
Chemical compound
Vanadyl sulfate
Vanadyl sulfate trihydrate

Vanadyl(IV) sulfate describes a collection of inorganic compounds of vanadium with the formula, VOSO4(H2O)x where 0 ≤ x ≤ 6. The pentahydrate is common. This hygroscopic blue solid is one of the most common sources of vanadium in the laboratory, reflecting its high stability. It features the vanadyl ion, VO2+, which has been called the "most stable diatomic ion".[1]

Vanadyl sulfate is an intermediate in the extraction of vanadium from petroleum residues, one commercial source of vanadium.[2]

Synthesis, structure, and reactions

Vanadyl sulfate is most commonly obtained by reduction of vanadium pentoxide with sulfur dioxide:

V2O5 + 7 H2O + SO2 + H2SO4 → 2 [V(O)(H2O)4]SO4

From aqueous solution, the salt crystallizes as the pentahydrate, the fifth water is not bound to the metal in the solid. Viewed as a coordination complex, the ion is octahedral, with oxo, four equatorial water ligands, and a monodentate sulfate.[1][3] The trihydrate has also been examined by crystallography.[4] A hexahydrate exists below 13.6 °C (286.8 K).[5] Two polymorphs of anhydrous VOSO4 are known.[6]

The V=O bond distance is 160 pm, about 50 pm shorter than the V–OH2 bonds. In solution, the sulfate ion dissociates rapidly.

Being widely available, vanadyl sulfate is a common precursor to other vanadyl derivatives, such as vanadyl acetylacetonate:[7]

[V(O)(H2O)4]SO4 + 2 C5H8O2 + Na2CO3 → [V(O)(C5H7O2)2] + Na2SO4 + 5 H2O + CO2

In acidic solution, oxidation of vanadyl sulfate gives yellow-coloured vanadyl(V) derivatives. Reduction, e.g. by zinc, gives vanadium(III) and vanadium(II) derivatives, which are characteristically green and violet, respectively.

Occurrence in nature

Like most water-soluble sulfates, vanadyl sulfate is only rarely found in nature. Anhydrous form is pauflerite,[8] a mineral of fumarolic origin. Hydrated forms, also rare, include hexahydrate (stanleyite), pentahydrates (minasragrite, orthominasragrite,[9] and anorthominasragrite) and trihydrate - bobjonesite.[10]

Medical research

Vanadyl sulfate is a component of food supplements and experimental drugs. Vanadyl sulfate exhibits insulin-like effects.[11]

Vanadyl sulfate has been extensively studied in the field of diabetes research as a potential means of increasing insulin sensitivity. No evidence indicates that oral vanadium supplementation improves glycaemic control.[12][13] Treatment with vanadium often results in gastrointestinal side-effects, primarily diarrhea.

Vanadyl sulfate is also marketed as a health supplement, often for bodybuilding. Deficiencies in vanadium result in reduced growth in rats.[14] Its effectiveness for bodybuilding has not been proven; some evidence suggests that athletes who take it are merely experiencing a placebo effect.[15]

References

  1. ^ a b Greenwood, Norman N.; Earnshaw, Alan (1984). Chemistry of the Elements. Oxford: Pergamon Press. p. 1157. ISBN 978-0-08-022057-4.
  2. ^ Günter Bauer; Volker Güther; Hans Hess; Andreas Otto; Oskar Roidl; Heinz Roller; Siegfried Sattelberger (2005). "Vanadium and Vanadium Compounds". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a27_367. ISBN 3-527-30673-0.
  3. ^ Tachez, M.; Theobald, F.R. (1980). "Structure du Sulfate de Vanadyle Pentahydrate VO(H2O)5SO4 beta (variete orthorhombique)". Acta Crystallographica B. B36 (8): 1757–p1761. Bibcode:1980AcCrB..36.1757T. doi:10.1107/S0567740880007170.
  4. ^ Tachez, M.; Theobald, F. R. (1980). "Liaisons hydrogene dans les cristaux de sulfate de vanadyle trihydrate VOSO4(H2O)3: Comparaison structurale de quatre sulfates de vanadyle hydrate". Acta Crystallographica B. 36 (12): 2873–2880. Bibcode:1980AcCrB..36.2873T. doi:10.1107/S056774088001045X.
  5. ^ M. Tachez, F. Theobald, G. Trouillot. Crystal data for vanadyl sulphate hexahydrate VOSO4.6H2O. J. Appl. Crystallogr. (1976). 9, 246
  6. ^ Boghosian, S.; Eriksen, K.M.; Fehrmann, R.; Nielsen, K. (1995). "Synthesis, Crystal Structure Redetermination and Vibrational Spectra of beta- VOSO4". Acta Chemica Scandinavica. 49: 703–708. doi:10.3891/acta.chem.scand.49-0703.Longo, J. M.; Arnott, R. J. (1970). "Structure and magnetic properties of VOSO4". Journal of Solid State Chemistry. 1 (3–4): 394–p398. Bibcode:1970JSSCh...1..394L. doi:10.1016/0022-4596(70)90121-0.
  7. ^ Bryant, Burl E.; Fernelius, W. Conard (1957), "Vanadium(IV) Oxy(acetylacetonate)", Inorganic Syntheses, vol. 5, pp. 113–16, doi:10.1002/9780470132364.ch30, ISBN 978-0-470-13236-4
  8. ^ Krivovichev, S. V.; Vergasova, L. P.; Britvin, S. N.; Filatov, S. K.; Kahlenberg, V.; Ananiev, V. V. (1 August 2007). "Pauflerite, -VO(SO4), a New Mineral Species from the Tolbachik Volcano, Kamchatka Peninsula, Russia". The Canadian Mineralogist. 45 (4): 921–927. Bibcode:2007CaMin..45..921K. doi:10.2113/gscanmin.45.4.921.
  9. ^ Hawthorne, F. C.; Schindler, M.; Grice, J. D.; Haynes, P. (1 October 2001). "Orthominasragrite, V4+O(SO4)(H2O)5, A New Mineral Species from Temple Mountain, Emery County, Utah, U.A.A.". The Canadian Mineralogist. 39 (5): 1325–1331. Bibcode:2001CaMin..39.1325H. doi:10.2113/gscanmin.39.5.1325.
  10. ^ Schindler, M.; Hawthorne, F. C.; Huminicki, D. M.C.; Haynes, P.; Grice, J. D.; Evans, H. T. (1 February 2003). "Bobjonesite, V4+ O (So4) (H2O)3, A New Mineral Species from Temple Mountain, Emery County, Utah, U.s.a.". The Canadian Mineralogist. 41 (1): 83–90. Bibcode:2003CaMin..41...83S. doi:10.2113/gscanmin.41.1.83.
  11. ^ Crans, D. C.; Trujillo, A. M.; Pharazyn, P. S.; Cohen, M. D. (2011). "How environment affects drug activity: Localization, compartmentalization and reactions of a vanadium insulin-enhancing compound, dipicolinatooxovanadium(V)". Coord. Chem. Rev. 255 (19–20): 2178–2192. doi:10.1016/j.ccr.2011.01.032.
  12. ^ Yeh, Gloria Y.; Eisenberg, David M.; Kaptchuk, Ted J.; Phillips, Russell S. (2003). "Systematic Review of Herbs and Dietary Supplements for Glycemic Control in Diabetes". Diabetes Care. 26 (4): 1277–1294. doi:10.2337/diacare.26.4.1277. PMID 12663610.
  13. ^ Smith, D.M.; Pickering, R.M.; Lewith, G.T. (31 January 2008). "A systematic review of vanadium oral supplements for glycaemic control in type 2 diabetes mellitus". QJM. 101 (5): 351–358. doi:10.1093/qjmed/hcn003. PMID 18319296.
  14. ^ Schwarz, Klaus; Milne, David B. (1971). "Growth Effects of Vanadium in the Rat". Science. 174 (4007): 426–428. Bibcode:1971Sci...174..426S. doi:10.1126/science.174.4007.426. JSTOR 1731776. PMID 5112000. S2CID 24362265.
  15. ^ Talbott, Shawn M.; Hughes, Kerry (2007). "Vanadium". The Health Professional's Guide to Dietary Supplements. Lippincott Williams & Wilkins. pp. 419–422. ISBN 978-0-7817-4672-4.
  • v
  • t
  • e
Vanadium(0)
  • V(CO)6
Vanadium(II)
  • VF2
  • VBr2
  • VCl2
  • VI2
  • VO
  • VS
  • VSO4
Vanadium(III)
  • VBr3
  • VCl3
  • VF3
  • VI3
  • VN
  • V2O3
  • V2(SO4)3
  • V2S3
Organovanadium(III) compounds
  • V(C9H11)3
  • Vanadium(IV)
    • VC
    • VO2
    • VOCl2
    • V(S2)2
    • VCl4
    • VF4
    Organovanadium(IV) compounds
  • VO(C5H7O2)2
  • Vanadyl(IV) compounds
    • VOSO4
    Vanadium(V)
    • V2O5
    • VOCl3
    • VOF3
    • VO2F
    • VF5
    • VCl5
    • NH4VO3
    • VOPO4
    • VO+2
    Vanadyl(V) compounds
    • VO(ClO4)3
    • VO(NO3)3
    • v
    • t
    • e
    Mineral supplements (A12)
    Major
    Calcium#
    Magnesium
    Phosphorus
    Potassium
    Sodium
    Sulfur
    Trace
    Copper
    Iodine
    Iron
    • (II) fumarate
    • (II) sulfate#
    Selenium
    Zinc
    Ultratrace
    Chromium
    • (III) picolinate
    • (III) chloride
    Fluorine
    Lithium
    Vanadium
    • (IV) sulfate
    • v
    • t
    • e
    Compounds containing the sulfate group (SO2−4)
    H2SO4 He
    Li2SO4 BeSO4 B2S2O9
    -BO3
    +BO3
    esters
    ROSO3
    (RO)2SO2
    +CO3
    +C2O4
    (NH4)2SO4
    [N2H5]HSO4
    (NH3OH)2SO4
    NOHSO4
    +NO3
    HOSO4 +F Ne
    Na2SO4
    NaHSO4
    MgSO4 Al2(SO4)3
    Al2SO4(OAc)4
    Si +PO4 SO2−4
    HSO3HSO4
    (HSO4)2
    +SO3
    +Cl Ar
    K2SO4
    KHSO4
    CaSO4 Sc2(SO4)3 TiOSO4 VSO4
    V2(SO4)3
    VOSO4
    CrSO4
    Cr2(SO4)3
    MnSO4 FeSO4
    Fe2(SO4)3
    CoSO4
    Co2(SO4)3
    NiSO4
    Ni2(SO4)3
    CuSO4
    Cu2SO4
    [Cu(NH3)4(H2O)]SO4
    ZnSO4 Ga2(SO4)3 Ge As +SeO3 Br Kr
    RbHSO4
    Rb2SO4
    SrSO4 Y2(SO4)3 Zr(SO4)2 Nb2O2(SO4)3 MoO(SO4)2
    MoO2(SO4)
    Tc Ru(SO4)2 Rh2(SO4)3 PdSO4 Ag2SO4
    AgSO4
    CdSO4 In2(SO4)3 SnSO4
    Sn(SO4)2
    Sb2(SO4)3 Te +IO3 Xe
    Cs2SO4
    CsHSO4
    BaSO4 * Lu2(SO4)3 Hf Ta WO(SO4)2 Re2O5(SO4)2 OsSO4
    Os2(SO4)3
    Os(SO4)2
    IrSO4
    Ir2(SO4)3
    Pt2(SO4)54– AuSO4
    Au2(SO4)3
    Hg2SO4
    HgSO4
    Tl2SO4
    Tl2(SO4)3
    PbSO4
    Pb(SO4)2
    Bi2(SO4)3 PoSO4
    Po(SO4)2
    At Rn
    Fr RaSO4 ** Lr Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
     
    * La2(SO4)3 Ce2(SO4)3
    Ce(SO4)2
    Pr2(SO4)3 Nd2(SO4)3 Pm2(SO4)3 Sm2(SO4)3 EuSO4
    Eu2(SO4)3
    Gd2(SO4)3 Tb2(SO4)3 Dy2(SO4)3 Ho2(SO4)3 Er2(SO4)3 Tm2(SO4)3 Yb2(SO4)3
    ** Ac2(SO4)3 Th(SO4)2 Pa U2(SO4)3
    U(SO4)2
    UO2SO4
    Np(SO4)2 Pu(SO4)2 Am2(SO4)3 Cm2(SO4)3 Bk Cf2(SO4)3 Es Fm Md No